materials

Review
Crystal Structure Formation of
CH3NH3PbI3-xClx Perovskite
Shiqiang Luo and Walid A. Daoud *
School of Energy and Environment, City University of Hong Kong, Tat Chee Avenue, Hong Kong, China;
sqluo3-c@my.cityu.edu.hk
* Correspondence: wdaoud@cityu.edu.hk; Tel.: +852-3442-4499

Academic Editor: Joshua M. Pearce

Received: 11 December 2015; Accepted: 16 February 2016; Published: 24 February 2016

Abstract: Inorganic-organic hydride perovskites bring the hope for fabricating low-cost and
large-scale solar cells. At the beginning of the research, two open questions were raised: the hysteresis
effect and the role of chloride. The presence of chloride significantly improves the crystallization
and charge transfer property of the perovskite. However, though the long held debate over of the
existence of chloride in the perovskite seems to have now come to a conclusion, no prior work has
been carried out focusing on the role of chloride on the electronic performance and the crystallization
of the perovskite. Furthermore, current reports on the crystal structure of the perovskite are rather
confusing. This article analyzes the role of chloride in CH3 NH3 PbI3-x Clx on the crystal orientation and
provides a new explanation about the (110)-oriented growth of CH3 NH3 PbI3 and CH3 NH3 PbI3-x Clx .

Keywords: solar cells; perovskites; X-ray diffraction; phase transitions

1. Introduction
Since the first organic-inorganic halide perovskite solar cell was reported [1], perovskites have
attracted growing interest and the power conversion efficiency (PCE) has reached 20.1% [2]. It is
not very common that a photovoltaic device can experience such a rapid development. While the
structure of the cells evolved from sensitized meso-structure to planar structure [3], both inorganic
and organic materials can be applied as electron and hole transfer materials [4]. Furthermore, by
tuning the composition of the perovskite, the band gap can be easily modified [5]. Given the numerous
advantages of perovskite, a clear understanding of the crystal structure is crucial and the role of
chloride in the formation of CH3 NH3 PbI3-x Clx (hereafter, we use MA short for CH3 NH3 ) is one of the
most pressing topics.
It has been reported that the presence of chloride in the perovskite improves the uniformity of its
layer [6] and results in an increase of the carriers’ diffusion length from ca. 100 nm to over 1 µm [7].
However, the long held debate over of the existence of chloride in the perovskite seems to have now
come to a conclusion. First, when synthesizing the perovskite by the one step method with precursor
solution of MACl and PbI2 (1:1 molar ratio) in anhydrous N,N-dimethylformamide (DMF), the resulting
crystal is not MAPbI2 Cl but a mixture of MAPbI3 and MAPbCl3 [8]. This provides direct evidence
that chloride (Cl´ ) cannot substitute iodine (I´ ) in the perovskite to form a stable crystal. Then, two
contradictory results were then reported. X-ray photoelectron spectroscopy (XPS) showed that the molar
ratio C:N:Pb:I:Cl of the perovskite is ca. 1:1:1:2:1, when prepared from a precursor of MAI:PbCl2 (molar
ratio 3:1) [9]. On the other hand, energy dispersive X-ray (EDX) analysis showed that no Cl´ was present
in the perovskite prepared from PbI2 + MAI + MACl [10]. Noting that the XPS was unable to determine
the existence of MAPbI2 Cl crystal and that EDX has its detecting limitation, more precise characterizations
were needed. Later on, the simultaneous Fourier transform infrared spectroscopy analysis of the expelled

Materials 2016, 9, 123; doi:10.3390/ma9030123 www.mdpi.com/journal/materials

Materials 2016, 9, 123 2 of 13

gas during the decomposition of MAPbI3-x Clx showed the presence of Cl´ , angle-resolved XPS [11] and
X-ray fluorescence spectroscopy (XFS) [12] not only confirmed the existence of Cl´ , but also showed that
Cl´ was located at the interface between the perovskite and the electron transport TiO2 layer, and not in the
perovskite structure [11,12]. Moreover, scanning transmission microscopy-energy dispersive spectroscopy
(STEM-EDS) detected no trace of Cl´ in the perovskite. Even though there is a strong Cl´ signal, no N
was observed indicting the presence of only PbCl2 [13]. Thus, Cl´ only appears at the interface between
MAPbI3 and the anode. Two more reports have further confirmed this conclusion. XPS analysis showed
only weak Cl´ signal after etching the surface of MAPbI3-x Clx by a 50 nm thickness [14]. Hard X-ray
photoelectron spectroscopy and fluorescence yield X-ray absorption spectroscopy showed no Cl´ at the
surface of MAPbI3-x Clx with higher average concentration of Cl throughout the perovskite layer at the
deep beneath [15]. Here, we refer to MAPbI3-x Clx as MAPbI3 that is prepared using chloride-containing
precursors. However, as the condition for depositing MAPbI3-x Clx differs, Cl´ may still remain in the
resulting perovskite layer. For instance, X-ray absorption near edge structure (XANES) results showed
that x = 0.05 ˘ 0.03 Cl atoms per formula unit remain in the films after annealing at 95 ˝ C for 120 min [16].
The results from photothermal induced resonance (PTIR) showed that the MAPbI3-x Clx film consists of a
mixture of Cl-rich (xlocal < 0.3) and Cl-poor phases after a mild annealing (60 ˝ C, 60 min) and homogeneous
Cl-poorer (xlocal < 0.06) phase upon further annealing (110 ˝ C) [17].
In addition, first-principles calculation results provide some good explanation. For the crystal
structure, Cl´ concentration was found below 3%–4% [8] and if the Cl´ ions enter the crystal structure,
they preferentially occupy the apical positions in the PbI4 X2 octahedra [18]. For the electronic property,
while the molecular orientations of CH3 NH3 + result in three times larger photocurrent response than
the ferroelectric photovoltaic BiFeO3 , Cl´ substitution at the equatorial site induces a larger response
than does substitution at the apical site [19]. Results also showed that, using Cl´ precursor can avoid
forming the PbI defects [20]. Introducing Cl´ would reduce the lattice constant which can inhibit the
formation of interstitial defects [21]. As excitons may be screened by collective orientational motion
of the organic cations, Cl´ might hinder this motion and results in better transport properties [22].
Little difference of electronic properties was represent among orthorhombic, tetragonal and cubic
phases of MAPbI3 [23], however, the valance-band-maximum and conduction-band-minimum states
can be mainly derived from iodine ions at some unique positions, Cl´ substitution can strengthen
the unique position of the ions and result in more localized charge density [24]. Thus, lower carrier
recombination rate and enhanced carrier transport ensued. For the interface, the (001) and (110) surfaces
tend to favor hole injection to 2,21 ,7,71 -tetrakis(N,N-di-p-methoxyphenylamine)-9,91 -spirobifluorene
(Spiro-MeOTAD), while the (100) surface facilitates electron transfer to [6,6]-phenyl C61 -butyric acid
methyl ester (PCBM) [25]. A better structural matching between adjacent rows of perovskite surface
halides and TiO2 under coordinated titanium may be the reason for the (110)-oriented growth of
MAPbI3-x Clx and MAPbI3 [26]. Interfacial Cl´ may thus further stabilize the (110) surface and modify
the interface electronic structure between MAPbI3 and TiO2 [26].
Despite the absence of Cl´ in the perovskite, it still played an important role in the crystallization
process. For instance, the morphology of MAPbI3-xClx was compared with MAPbI3 [27] and a model in
which the Cl´ rich phase modifies the morphologies of perovskite was proposed and fit well with the results
from scanning electron microscopy (SEM) [27]. In addition, the transmission electron microscopy (TEM) of
freeze-dried perovskite MAPbI3-xClx precursor solution showed the presence of PbCl2 nanoparticles [28]
and this is in agreement with the dynamic light scattering (DLS) investigations of MAPbI3-xClx precursor
solution [29]. Thus, references [28,29] further proved the model of the heterogeneous nucleation by PbCl2
nanoparticles proposed in reference [27]. However, the formation mechanism of the crystal structure remains
undermined and this will be discussed in the following parts of this article.

2. Methods for Fabricating MAPbI3-x Clx

In Section 3, we discuss the crystal structure of MAPbI3-x Clx according to the deposition method.
As the fabrication methods were discussed in detail in reference [30], here we add a brief introduction
Materials 2016, 9, 123 3 of 13

about the preparation methods of MAPbI3-x Clx . For the one-step deposition method, MAI:PbI2 /PbCl2
(molar ratio 1:1 or 3:1) [31,32] were dissolved in γ-butyrolactone (GBL) or DMF, spin-coated on
the substrates and annealed to form perovskite. Different annealing conditions result in different
morphology of the MAPbI3-x Clx layer. While a rapid thermal annealing at 130 ˝ C resulted in micron-sized
Materials 2016, 9, 123  3 of 13 
perovskite grains [33], two-step annealing, such as 90 ˝ C for 30 min then at 100 ˝ C for 2 min [34]
or 60 ˝ C then ramping
MAI:PbI to 90
2/PbCl2  (molar 
˝ C [35], resulted in optimal PCE on poly(3,4-ethylenedioxythiophene)
ratio  1:1  or  3:1)  [31,32]  were  dissolved  in  γ‐butyrolactone  (GBL)  or  DMF, 
spin‐coated on the substrates and annealed to form perovskite. Different annealing conditions result 
poly(styrene-sulfonate) (PEDOT:PSS) substrates. A full coverage of perovskite can be achieved by rapid
cooling in different morphology of the MAPbI
after annealing [36]. To increase the 3‐xClx layer. While a rapid thermal annealing at 130 °C resulted 
solubility of Cl´ , 1,8-diiodooctane [37] or other alkyl halide
in micron‐sized perovskite grains [33], two‐step annealing, such as 90 °C for 30 min then at 100 °C 
additives [38] or dimethyl sulfoxide [9] can be employed. Adding poly-(vinylpyrrolidone) (PVP) can
for  2  min  [34]  or  60  °C  then  ramping  to  90  °C  [35],  resulted  in  optimal  PCE  on 
also improve the surface coverage of perovskite [39]. It is interesting to note that, for MAPbI3-x Clx , a
poly(3,4‐ethylenedioxythiophene) poly(styrene‐sulfonate) (PEDOT:PSS) substrates. A full coverage 
simple annealing step is enough to form a good coverage [6,40], but for MAPbI3 , a special step,−, such as
of perovskite can be achieved by rapid cooling after annealing [36]. To increase the solubility of Cl
multi-deposition [41], adding N-cyclohexyl-2-pyrrolidone (CHP) [42], fast deposition [43–45], or air flow
1,8‐diiodooctane [37] or other alkyl halide additives [38] or dimethyl sulfoxide [9] can be employed. 
Adding 
during spin poly‐(vinylpyrrolidone) 
coating [46,47], is needed.(PVP)  can  also  improve  the  surface  coverage  of  perovskite  [39].   
It  is  interesting 
The sequential depositionto  note  that, method
for  MAPbI was3−xClx,  a  simple  annealing  step  is  enough  to  form  a  good   
mainly applied for MAPbI3 perovskite. In a typical
coverage  [6,40],  but  for  MAPbI3,  a  special  step,  such  as  multi‐deposition  [41],  adding 
synthesis, the solution of PbI2 in DMF was spun on a substrate as the first step then the substrate
N‐cyclohexyl‐2‐pyrrolidone  (CHP)  [42],  fast  deposition  [43–45],  or  air  flow  during  spin   
was dipped in a solution of MAI in 2-propanol (IPA) to form MAPbI3 crystals as the second step [48].
coating [46,47], is needed. 
For the inclusion of chloride,
The  sequential  in themethod 
deposition  first step was the PbClapplied 
mainly  2 can be mixed
for  MAPbI with PbI2 in DMF
3  perovskite.  or dimethyl
In  a  typical 
sulfoxide (DMSO) [49–52], and/or
synthesis, the solution of PbI the second step MACl can be added [53–55]. For vapor based
2 in DMF was spun on a substrate as the first step then the substrate was 

dipped in a solution of MAI in 2‐propanol (IPA) to form MAPbI
deposition methods, the MAPbI3-x Clx can be formed by co-evaporating 3 crystals as the second step [48].   
MAI and PbCl2 onto the
For the inclusion of chloride, in the first step the PbCl2 can be mixed with PbI2 in DMF or dimethyl 
substrates [56,57] or by reacting PbCl2 on substrates with MAI vapor [58,59].
sulfoxide  (DMSO)  [49–52],  and/or  the  second  step  MACl  can  be  added  [53–55].  For  vapor  based 
deposition  methods,  the  MAPbI3‐xClx  can  be  formed  by  co‐evaporating  MAI  and  PbCl2  onto  the 
3. The Crystal Structure Form and Formation
substrates [56,57] or by reacting PbCl2 on substrates with MAI vapor [58,59]. 
3.1. Crystal Structure of MAPbI3 Layer
3. The Crystal Structure Form and Formation 
The parameters and transitions of phases of bulk MAPbI3 were included in references [60,61].
3.1. Crystal Structure of MAPbI3 Layer 
Here, we focus on the tetragonal and cubic phases [62]. In fact, there are no critical differences between
The parameters and transitions of phases 
the two phases, except a slight rotation of PbI6 octahedra of  bulk  MAPbI 3 were included in references [60,61]. 
along the c-axis. The atomic structures of
Here,  we  focus  on  the  tetragonal  and  cubic  phases  [62].  In  fact,  there  are  no  critical  differences 
MAPbI3 of the two phases are shown in Figure 1A,B. Thus, the tetragonal phase can be treated as
between  the  two  phases,  except  ? a  slight  rotation  of  PbI6  octahedra  along  the  c‐axis.  The  atomic 
a pseudocubic phase with
structures of MAPbI a* = a/ 2, c* = c/2 [63]. Below 54 ˝ C, the cubic phase of MAPbI3 can be
3 of the two phases are shown in Figure 1A,B. Thus, the tetragonal phase can be 
transformed into the tetragonal phase [60], and the opposite transition occurs by annealing at3  100 ˝ C
treated as a pseudocubic phase with a* = a/√2, c* = c/2 [63]. Below 54 °C, the cubic phase of MAPbI
for 15 min [41]. In Figure 1C, the X-ray diffraction (XRD) patterns of the two phases are shown. After
can be transformed into the tetragonal phase [60], and the opposite transition occurs by annealing at 
100  °C  for 
transformation to15 the
min  [41].  In  Figure 
tetragonal 1C,  the
phase, the  X‐ray 
(100) diffraction 
and (200)(XRD) 
peakspatterns 
of cubicof  the 
MAPbItwo  phases  are 
3 split, also new
shown. After transformation to the tetragonal phase, the (100) and (200) peaks of cubic MAPbI
(211) and (213) peaks show up. Here, we use the peak splitting as indictor for phase transformation. 3 split, 

also  new  (211)  and  (213)  peaks  show  up.  Here,  we  use  the  peak  splitting  as  indictor  for  phase 
Analysis of the MAPbI3-x Clx usually shows the cubic phase of MAPbI3 , however, with a much more
transformation.  Analysis  of  the  MAPbI3‐xClx  usually  shows  the  cubic  phase  of  MAPbI3,  however, 
preference along (100) and (200). This will be discussed in the Sections 3.2 and 3.3.
with a much more preference along (100) and (200). This will be discussed in the Sections 3.2 and 3.3.   

 
Figure 1. Cont. 
Figure 1. Cont.
Materials 2016, 9, 123 4 of 13
Materials 2016, 9, 123  4 of 13 

 
Figure  1.  (A)  Atomic  models  of  MAPbI3  with  cubic  phase;  and  (B)  tetragonal  phase;  (C)  the 
Figure 1. (A) Atomic models of MAPbI with cubic phase; and (B) tetragonal phase; (C) the calculated
calculated XRD patterns for MAPbI33 in both phases. (A) and (B) are reprinted from reference [64], 
XRD patterns for MAPbI3 in both phases. (A) and (B) are reprinted from reference [64], Copyright ©
Copyright © IOP Publishing. Reproduced with permission. All rights reserved; (C) is reprinted from 
IOP Publishing. Reproduced with permission. All rights reserved; (C) is reprinted from reference [65],
reference [65], Copyright © 2013, Royal Society of Chemistry. 
Copyright © 2013, Royal Society of Chemistry.
Another  phase  which  should  be  noted  is  the  amorphous  phase.  Pair  distribution  function 
analysis 
Another phaseof  X‐ray 
whichscattering 
shouldshowed 
be noted that  after 
is the annealing  at 
amorphous 100  °C 
phase. for distribution
Pair 30  min,  the  MAPbI
function 3  in 
analysis
meso‐porous TiO2 has about 30 atom% in medium range crystalline order and the other 70 atom% in 
˝
of X-ray scattering showed that after annealing at 100 C for 30 min, the MAPbI3 in meso-porous TiO2
a disordered state with a coherence length of 1.4 nm [66]. The poor crystallization of the MAPbI3 in 
has about 30 atom% in medium range crystalline order and the other 70 atom% in a disordered state
meso‐porous  TiO2  was  studied  by  high‐resolution  TEM  [67].  Quartz  crystal  microbalance 
with a coherence length of 1.4 nm [66]. The poor crystallization of the MAPbI
measurements suggest that during the sequential method only half of PbI 3 in meso-porous
2 is converted to MAPbI 3 
TiO2
was studied by high-resolution TEM [67]. Quartz crystal microbalance measurements
instantly, while the other half is involved in reversible transformation with MAPbI suggest that
3. Additionally, 

the  sequential
during the amorphous  method
character only
with half
a  very  small 
of PbI 2 isaverage  crystallite 
converted to MAPbIsize  3may  be  present 
instantly, whileafter 
the the 
other half
transformation  as  previously  discussed  [68].  The  amorphous  phase  may  also 
is involved in reversible transformation with MAPbI3 . Additionally, the amorphous character with a present  during  the 
initially deposited MAPbI3‐xClx, as indicated by the envelope in some XRD spectra. In reference [69], 
very small average crystallite size may be present after the transformation as previously discussed [68].
the amorphous phase MA5PbCl4I3 was also mentioned. Moreover, both XRD and photoluminescence 
The amorphous phase 2may
studies of MAPbI also present
Cl (2MAPbI during the initially deposited MAPbI3-x Clx , as indicated by
3+MAPbCl3) indicate the existence of the amorphous phase [70]. 
the envelope in some XRD spectra. In reference [69], the amorphous phase MA5 PbCl4 I3 was also
3.2. Converting Lead Halides to Perovskite 
mentioned. Moreover, both XRD and photoluminescence studies of MAPbI2 Cl (2MAPbI3 +MAPbCl3 )
indicate theIn the sequential deposition method, PbI
existence of the amorphous phase 2[70]. or/and PbCl2 were first dissolved in a solvent. As PbI2 
crystal has a layered structure, DMF can intercalate into the PbI2 interlayer space and screen PbI2 via 
3.2. Converting Lead Halides to Perovskite
Pb‐O bonding [71–73]. When DMF is intercalated, the XRD peak of the PbI2 (001) plane red shifts 

from 14.8° to 7.94° [72,73]. The red‐shift of this XRD peak to 9.17° also indicates the intercalation of 
In the sequential deposition method, PbI2 or/and PbCl2 were first dissolved in a solvent. As PbI2
DMSO [43]. While PbCl2 doesn’t possess a similar layered structure as PbI2, its solubility is poor where 
crystal has
PbCla2layered structure, DMF can intercalate into the PbI2 interlayer space and screen PbI
 nanoparticles may only suspend in the solvent [28]. However, depositing a mixture of PbI 2 via Pb-O
2 and 

bondingPbCl
[71–73]. When DMF is intercalated, the XRD peak of the PbI2 (001) plane red shifts from ˝
2 on the substrates result in a new PbICl phase [74], whose crystal structure is similar to PbCl 2 [75]. 14.8 to

7.94˝ [72,73].At  the red-shift

The beginning 
of of 
thisthe 
XRDreaction 
peakof 
toPbI
9.17 ˝ also
2  and  MAI,  a  predominant 
indicates peak  at  (220) 
the intercalation of DMSOappeared 
[43].  While
(as shown in Figure 2B). In other words, the MAPbI 3 preferentially grows along (220) plane at first. 
PbCl2 doesn’t possess a similar layered structure as PbI2 , its solubility is poor where PbCl2 nanoparticles
The annealing process increases the long range crystalline order and results in the predominant (110) 
may only suspend in the solvent [28]. However, depositing a mixture of PbI2 and PbCl2 on the substrates
peak instead. Noting the (220) is only a short range of (110), thus, another possible reason for the 
result in(110)‐oriented growth of MAPbI
a new PbICl phase [74], whose crystal structure is similar to PbCl2 [75].
3‐xClx and MAPbI3 may be because layered crystal structure of PbI 2 
At (growth along (001) planes of PbI
the beginning of the reaction 2of PbI2 and MAI, a predominant peak at (220) appeared (as shown
 like the liquid catalyst cluster model mentioned in reference [76]). 
in Figure 2B). In other words, the MAPbI33 are showed in Figure 3. 
The lattice planes of tetragonal MAPbI preferentially grows along (220) plane at first. The annealing
process increases the long range crystalline order and results in the predominant (110) peak instead.
Noting the (220) is only a short range of (110), thus, another possible reason for the (110)-oriented
growth of MAPbI3-x Clx and MAPbI3 may be because layered crystal structure of PbI2 (growth along
(001) planes of PbI2 like the liquid catalyst cluster model mentioned in reference [76]). The lattice
planes of tetragonal MAPbI3 are showed in Figure 3.
Materials 2016, 9, 123 5 of 13

Materials 2016, 9, 123  5 of 13 

Materials 2016, 9, 123  5 of 13 

 
Figure 2. XRD patterns of glass substrates with vapor deposition of (A) a layer of PbI2; and (B) a layer   
Figure 2. XRD patterns of glass substrates with vapor deposition of (A) a layer of PbI2 ; and (B) a layer
of  PbI2  followed  by  a  layer  of  MAI,  repeating  this  step  7  times;  XRD  pattern  of  the  (C)  annealed 
of PbIFigure 2. XRD patterns of glass substrates with vapor deposition of (A) a layer of PbI
2 followed by a layer of MAI, repeating this step 7 times; XRD pattern of the 2(C) ; and (B) a layer 
annealed 7-time
7‐time deposited PbI 2/MAI layer; (D) 1‐time deposited PbI2 (50 nm thickness)/MAI (50 nm thickness) 
of  PbI2  followed  by  a  layer  of  MAI,  repeating  this  step  7  times;  XRD  pattern  of  the  (C)  annealed 
deposited PbI 2 /MAI layer;
layer;  and  (E)  1‐time  deposited  PbI2  (150  nm  thickness)/MAI  (150  nm  thickness)  layer.  Reprinted layer;
(D) 1-time deposited PbI 2 (50 nm thickness)/MAI (50 nm thickness)
7‐time deposited PbI 2/MAI layer; (D) 1‐time deposited PbI2 (50 nm thickness)/MAI (50 nm thickness) 
and (E) 1-time deposited PbI2 (150 nm thickness)/MAI (150 nm thickness) layer. Reprinted from
from reference [77], Copyright © 2015, Royal Society of Chemistry. 
layer;  and  (E)  1‐time  deposited  PbI2  (150  nm  thickness)/MAI  (150  nm  thickness)  layer.  Reprinted 
reference [77], Copyright © 2015, Royal Society of Chemistry.
from reference [77], Copyright © 2015, Royal Society of Chemistry. 

 
 
Figure 3. Crystallographic (lattice) planes (in gray) of tetragonal MAPbI3. Reprinted from reference [78], 
Copyright © 2015, American Chemical Society. 
Figure 3. Crystallographic (lattice) planes (in gray) of tetragonal MAPbI3. Reprinted from reference [78], 
Figure 3. Crystallographic (lattice) planes (in gray) of tetragonal MAPbI3. Reprinted from reference [78],
Copyright © 2015, American Chemical Society. 
Copyright © 2015,
For PbCl American Chemical Society.
2, Cl− was detached from PbCl 2 when the PbCl2 was evaporated on the MAI substrate [79] 

and all the atoms of lead halide were dissociated during the crystal formation of the perovskite [80]. 
For PbCl2, Cl− was detached from PbCl2 when the PbCl2 was evaporated on the MAI substrate [79] 
For PbCl2 , Cl´ was detached from PbCl2 when the PbCl2 was evaporated on the MAI
and all the atoms of lead halide were dissociated during the crystal formation of the perovskite [80]. 
substrate [79] and all the atoms of lead halide were dissociated during the crystal formation of
the perovskite [80]. Thus, except the speed and the way of breaking the lead halide, the following
Materials 2016, 9, 123 6 of 13

steps should be similar with the one step method (Section 3.3) for converting PbI2 or PbCl2 with MAI
to the perovskite. However, the situation in the presence of MACl may be different. As less energy is
Materials 2016, 9, 123  6 of 13 
needed for MACl than MAI to undergo phase transition from solid to gas [69], it may be easier for
MACl thanThus, except the speed and the way of breaking the lead halide, the following steps should be similar 
MAI to diffuse into the PbI2 and cause the crystallization of perovskite [81]. However, as
Cl´ cannotwith  the  one  step  method 
be incorporated (Section 33.3) 
into MAPbI for  converting 
crystal structure, PbI2  or 
the PbCl2and
MAI   with MACl
MAI  to 
maythe  perovskite. 
compete with each
However, the situation in the presence of MACl may be different. As less energy is needed for MACl 
other to determine the result crystal, because only MAPbI3 or MAPbCl3 was formed when PbI2 was
than MAI to undergo phase transition from solid to gas [69], it may be easier for MACl than MAI to 
soaked in 80 mMinto 
diffuse  MAI the +PbI
402 mM MACl
and  cause  the orcrystallization 
in 40 mM MAI + 80 mM
of  perovskite  MACl,
[81].  respectively
However,  [80].
as  Cl−  cannot  be Thus, the
incorporation of some
incorporated  amount
into  MAPbI3of MACl
  crystal  managed
structure,  to modify
the  MAI  and  MACl  the morphology
may  compete  with of theother 
each  perovskite
to  and
resulted indetermine the result crystal, because only MAPbI
better performance of the solar cells. 3 or MAPbCl3 was formed when PbI2 was soaked 
in  80  mM  MAI  +  40  mM  MACl  or  in  40  mM  MAI  +  80  mM  MACl,  respectively  [80].  Thus,  the 
3.3. One incorporation of some amount of MACl managed to modify the morphology of the perovskite and 
Step Deposition of MAPbI3-x Clx
resulted in better performance of the solar cells.   
The better crystallization of MAPbI3-x Clx along (110) and (220) plane of the tetragonal phase
3.3. One Step Deposition of MAPbI3‐xClx 
or (100) and (200) planes of the cubic phase may be due to the lowered cubic-tetragonal phase
The better crystallization of MAPbI
transition temperature of MAPbI3-x Clx after 3‐xClx along (110) and (220) plane of the tetragonal phase or 
the incorporation of Cl´ [82]. A clear cubic-tetragonal
(100)  and  (200)  planes  of  the  cubic  phase  may  be  due  to  the  lowered  cubic‐tetragonal  phase 
phase transition temperature of MAPbI3 was detected by differential scanning calorimeter (DSC)
transition  temperature  of  MAPbI3−xClx  after  the  incorporation  of  Cl−  [82].  A  clear  cubic‐tetragonal 
analysis [65], however no such phase transition was observed for MAPbI 3-x Clx [83].
phase  transition  temperature  of  MAPbI3  was  detected  by  differential  scanning  calorimeter  To explain
(DSC) 
the absence of the phase transition for MAPbI3-x Clx , we first study the crystallization process of
analysis [65], however no such phase transition was observed for MAPbI 3−x Cl x  [83]. To explain the 
MAPbI3-x Clabsence  of  the  phase  transition  for  MAPbI3−xClx,  we  first  study  the  crystallization  process  of 
x by one step deposition method.
MAPbI3‐xClx by one step deposition method. 

 
Figure 4. XRD patterns and optical images (insets) of MAPbI3‐xClx film during annealing. Reprinted 
Figure 4. XRD patterns and optical images (insets) of MAPbI3-x Clx film during annealing. Reprinted
from reference [84], Copyright © 2015, American Chemical Society. 
from reference [84], Copyright © 2015, American Chemical Society.
Detail information about crystal formation process of MAPbI3 is summarized in reference [85]. 
For MAPbI 3‐xClx, the transformation from the intermediate phase to the perovskite is determined as 
Detail information about crystal formation process of MAPbI is summarized in reference [85]. For
3
MAPbI3-x Clx , the transformation from the intermediate phase to the perovskite is determined as 80 ˝ C
by in situ grazing incidence wide-angle X-ray scattering (GIWAXS) [86]. Figure 4 presents a clearer
picture of the crystal formation of MAPbI3-x Clx . The 15.7˝ and 31.5˝ peaks are associated with the (100)
and (200) diffraction peaks of MAPbCl3 [82]. These peaks were also observed in references [27,87,88].
In Figure 4, it is interesting to note that MAPbI3 was formed first for the as-spin coated film but
Materials 2016, 9, 123 7 of 13
Materials 2016, 9, 123  7 of 13 

converted to MAPbCl3 after annealing at 100 ˝ C for 10 min, and then MAPbCl3 was4 converted
80 °C by in situ grazing incidence wide‐angle X‐ray scattering (GIWAXS) [86]. Figure  presents  a back
to MAPbI after 45 min of annealing
clearer picture of the crystal formation of MAPbI
3 [84]. Further 3‐x annealing
Cl x would result in the decomposition
. The 15.7° and 31.5° peaks are associated with  of
MAPbI the 3 to
(100) 
PbI2and 
, but(200)  diffraction 
this occurred peaks 
after of  MAPbCl
conversion to the3  [82].  These  peaks 
intermediate phase were  also  observed 
to MAPbI in   
3 [89]. Because
MAPbClreferences [27,87,88]. In Figure 4, it is interesting to note that MAPbI3 was formed first for the as‐spin 
3 is in a cubic phase, we suppose that MAPbCl 3 may cause a template effect for the cubic
MAPbI coated film but converted to MAPbCl
phase. 3 after annealing at 100 °C for 10 min, and then MAPbCl3 was 
3
converted  back  to  MAPbI3  after  45  min  of  annealing  [84].  Further  annealing  would  result  in  the 
In addition, the MAI:PbI2 (molar ratio 3:1) precursor solution on compact TiO2 can also
decomposition  of  MAPbI3  to  PbI2,  but  this  occurred  after  conversion  to  the  intermediate  phase  to 
form MAPbI3 with a predominant (110) plane, but the annealing temperature need to be above
MAPbI3 [89]. Because MAPbCl3 is in a cubic phase, we suppose that MAPbCl3 may cause a template 
150 ˝effect for the cubic MAPbI
C [84,88,90]. The different sublimation temperature of MAI and MACl and the evidence of
3 phase.   
residue MAI or MACl in the resulting
In  addition,  the  MAI:PbI2 (molar ratio 3:1) perovskite may explain
precursor  solution the higher annealing
on  compact  temperature
TiO2  can also form 
needed for MAPbI [84,91].
MAPbI3  with  3a  predominant  (110)  plane,  but  the  annealing  temperature  need  to  be  above   
The XRD
150  °C  patterns
[84,88,90].  The ofdifferent 
the resulting MAPbI
sublimation  3-x Clx prepared
temperature  of  MAI from different
and  MACl  and chloride-containing
the  evidence  of 
residue are
precursors MAI  or  MACl  in in
summarized the  resulting 
Figure perovskite 
5. All the patternsmay  explain 
showedthe  higher  annealing 
predominant temperature 
crystallization along
needed for MAPbI
the (110) and (220) planes. 3 [84,91]. 
Interestingly, the (220) peak split at a high MACl (x = 2) concentration in
Figure 5BThe  XRD 
[27]. This patterns 
split wasof  the 
alsoresulting 
observed MAPbI 3‐xClx  prepared  from  different  chloride‐containing 
in reference [29]. In the sequential deposition method,
precursors are summarized in Figure 5. All the patterns showed predominant crystallization along 
the (110) and (220) crystallization preference may be due to an in situ transformation process [92] of
the (110) and (220) planes. Interestingly, the (220) peak split at a high MACl (x = 2) concentration in 
PbI2 to MAPbI3 , as discussed in Section 3.2. However, the PbI6 octahedra are more likely to be fully
Figure 5B [27]. This split was also observed in reference [29]. In the sequential deposition method, 
dissociated in the one step precursor solution. [29,93–95] As MACl does not fit in the MAPbI3 structure,
the (110) and (220) crystallization preference may be due to an in situ transformation process [92] of 
it could be possible that MACl may be expelled along the (110)
PbI2 to MAPbI3, as discussed in Section 3.2. However, the PbI planes of the MAPbI3 and that is why
6 octahedra are more likely to be fully 
the MAPbI 3-x Clxin always
dissociated  the  one  showed the (110)solution.[29,93–95] 
step  precursor  and (220) orientation preference.
As  MACl  does  not  This assumption
fit  in  the  MAPbIcan 3  be
proved by (220) peak split in Figure 5B, as excess of MACl breaks down the crystal range along
structure, it could be possible that MACl may be expelled along the (110) planes of the MAPbI 3 and (110)

planesthat is why the MAPbI
resulting in peak split. 3‐xClx always showed the (110) and (220) orientation preference. This assumption 
However, MAI can fit in the MAPbI3 structure, (110)-oriented growth
can be proved by (220) peak split in Figure 5B, as excess of MACl breaks down the crystal range along 
is just the result of cubic phase in high temperature (150 ˝ C in refereneces [84,88,90]). Surprisingly, a
main(110) 
XRDplanes 
peak resulting 
of (310) was in  peak  split.  However, 
observed for the one MAI  stepcan deposition
fit  in  the  MAPbI
prepared3  structure,  (110)‐oriented 
MAPbI3 [96]. The main
growth  is  just  the  result  of  cubic  phase  in  high  temperature  (150  °C  in  refereneces  [84,88,90]). 
peak of (310), which is distinct from the (110) peak, may have resulted from the fact that the MAI was
Surprisingly,  a  main  XRD  peak  of  (310)  was  observed  for  the  one  step  deposition  prepared   
added into the precursor solution after the PbI2 was completely dissolved instead of both MAI and
MAPbI3 [96]. The main peak of (310), which is distinct from the (110) peak, may have resulted from 
PbI2 the fact that the MAI was added into the precursor solution after the PbI
being present at the same time [96], or the fact that the (310) plane of MAPbI3 may match the
2 was completely dissolved 
crystal structure of the substrate
instead of both MAI and PbI better. Then the magnitude of the (110) peak of MAPbI3-x Clx and
2 being present at the same time [96], or the fact that the (310) plane of 
the (310) peak of MAPbI
MAPbI3  may  match  the  further increasesof after
3 crystal  structure  5 weeks better. 
the  substrate  [96]. Thus,
Then  we
the  believe
magnitude  thatof the
the annealing
(110) 
process
peak may only reinforce
of  MAPbI 3‐xClx  and  the crystallization
the  (310)  peak  of  MAPbI preference
3  further  asincreases 
it is initially
after  5 formed andThus, 
weeks  [96].  the effects
we  of
believe that the annealing process may only reinforce the crystallization preference as it is initially 
substrate also contribute to the crystal structure formation of the perovskite in some cases. Returning
formed 
to Figure 5, ifand 
excessthe ofeffects 
MAClof  substrate 
breaks down also 
thecontribute 
growth along to  the 
thecrystal  structure 
(110) plane, formation 
we believe MACl of  the 
can also
perovskite  in  some  cases.  Returning  to  Figure  5,  if excess of MACl breaks down the growth along 
break down the crystalline order range. Since a large amount of MAPbI3 existed in the amorphous
the  (110)  plane,  we  believe  MACl  can  also  break  down  the  crystalline  order  range.  Since  a  large 
phase form, the cubic phase of MAPbI3 may be more favorable in short crystalline order range than
amount of MAPbI3 existed in the amorphous phase form, the cubic phase of MAPbI3 may be more 
the tetragonal phase.
favorable in short crystalline order range than the tetragonal phase. 

   
Figure  5.  XRD  patterns  of  MAPbI3‐xClx  prepared  from  (A)  precursor  solution  xPbCl2+yPbI2+zMAI   
Figure 5. XRD patterns of MAPbI3-x Clx prepared from (A) precursor solution xPbCl
(x = 0.25, 0.5, 0.75 and 1; y = 1 − x; z = 3 × x + y) in DMF; and (B) precursor solution 1PbI 2 +yPbI2 +zMAI
2+1MAI+xMACl 
(x = 0.25, 0.5, 0.75 and 1; y = 1 ´ x; z = 3 ˆ x + y) in DMF; and (B) precursor solution
(x = 0.5, 1, 1.5 and 2). Reprinted from reference [27], Copyright © 2014, American Chemical Society. 
1PbI2 +1MAI+xMACl (x = 0.5, 1, 1.5 and 2). Reprinted from reference [27], Copyright © 2014, American
Chemical Society.
Materials 2016, 9, 123 8 of 13

There are other influences associated with Cl´ . Increasing the temperature during the soaking of
the PbI2 substrate in MAI + MACl IPA solution can improve the (110) orientation of MAPbI3-x Clx where
the high temperature facilitates the expelling of MACl [97]. Annealing the MACl:PbI2 (3:1) precursor
on compact TiO2 at 60 ˝ C for 10 min followed by 100 ˝ C for 20 min instead of gradually heating from
25 to 100 ˝ C for 45 min resulted in the (200) crystal plane of MAPbI3-x Clx being vertically aligned
on the substrate [98]. The tetragonal phase MAPbI3-x Clx was occasionally found on compact TiO2
substrate [53], while the cubic phase always occurred in meso-porous substrate, where the trapped
MACl in meso-porous structure [8] helps the formation of cubic phase. While the size of MAPbI3
crystal grains are smaller but the degree of crystallinity improves in the presence of MACl [27,54], the
sequential deposited MAPbI3-x Clx results in (001) elongated crystals [13].

4. Conclusions
In this article, the location of Cl´ and its influence on the crystal morphology of MAPbI3-x Clx is
summarized, where the deposition methods (one step deposition, sequential deposition and vapor
based deposition) for MAPbI3-x Clx are reviewed. Furthermore, the cubic and tetragonal phases of
MAPbI3 are elucidated and the crystallization process of MAPbI3-x Clx is also summarized. Detailed
information about the crystal structure with variable deposition parameters is also discussed. Though a
recent report showed that Cl´ mainly improves the carrier transport at the perovskite/Spiro-MeOTAD
and perovskite/TiO2 interfaces, rather than within the perovskite crystals, the authors of reference [99]
more recently spatially resolved photoluminescence decay results showed less recombination in
the high chlorine concentration region [100]. Thus, the effect of high concentration of Cl´ on the
morphologies and electronic properties of the perovskite can still not be ignored. Additionally, whether
Cl´ is predominantly present as a substituent for I´ , as an interstitial, or at the surface of the crystal,
remains unclear [101] and this is worth further investigation.

Conflicts of Interest: The authors declare no conflict of interest.

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